CN108461308A - A kind of graphene/poly ion liquid composite material and preparation method and application - Google Patents
A kind of graphene/poly ion liquid composite material and preparation method and application Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of graphene/poly ion liquid composite material and preparation method and application, it is prepared for the ring-opening metathesis polymerization initiator containing pyrene functional group first, the graphene of initiator modification is obtained after by initiator and graphene dispersion in a solvent a period of time, using the graphene that initiator is modified as initiator, Grubbs second generations catalyst is added poly ion liquid monomer progress ring-opening metathesis polymerization and can be obtained graphene/poly ion liquid composite material as catalyst.The present invention, by the noncovalent interaction between polymer chain and graphene, can obtain the grapheme material of surface modification under conditions of not destroying graphene chemical constitution.
Description
Technical field
The invention belongs to field of composite material preparation, and in particular to a kind of graphene/poly ion liquid composite material and system
Preparation Method and application.
Background technology
Graphene is to pass through sp by single layer of carbon atom2The two-dimensional slice layer structure that hydridization is formed, is a kind of novel carbons
Nano material.It has the characteristics that excellent electrical property, mechanical property and thermal stability so that it is widely used as metallic crystal
Pipe, ultracapacitor, nonlinear optical material, nanocomposite carrier, electrochemical sensor, pharmaceutical carrier, hydrogen storage material,
Adsorbent, solar cell etc..However graphene film interlayer passes through stronger van der Waals interaction, it is easy to occur poly-
Collection, make its be insoluble in water and other there are commonly solvents, industrialized production to graphene and application all bring it is prodigious not
Just.In addition, the sp of graphene planes2Structure is stablized relatively, and chemism is poor so that the functional application of graphene also receives greatly
To limitation.
Traditional surface modification method can destroy the sp of graphene2Hybrid structure produces its mechanical performance and electric property
Raw certain influence.Chinese patent CN105289503A reports one kind by the oxygen-containing group such as hydroxyl on graphene oxide (GO)
The chemical bond joinings such as base, carboxyl, carbonyl together, by the surface of polymer chain covalence graft to GO, can prepare graphite
Alkene/polymer complex.But covalence graft method can destroy the original chemical constitution of graphene, to influence the machinery of graphene
Performance, electrical property etc..
For the deficiency of graphene surface modification method in the prior art, therefore, it is necessary to which further research is a kind of novel
Graphene surface modification method, do not changing graphene chemical constitution, while retaining graphene excellent performance, significantly improving
The dispersibility of graphene and its compatibility with matrix.
Invention content
In order to solve the deficiencies in the prior art, it is multiple that an object of the present invention is to provide a kind of graphene/poly ion liquid
Condensation material and preparation method and application can pass through polymer chain and graphite under conditions of not destroying graphene chemical constitution
Noncovalent interaction between alkene obtains the grapheme material of surface modification.
To achieve the goals above, the technical scheme is that：
The first aspect of the invention provides a kind of ring-opening metathesis polymerization (ROMP) initiator containing pyrene functional group,
Its structural formula is：
Initiator Zhong Bi functional groups can be acted on by non-covalent π-π and polymer one end is fixed on graphene, from
And avoid the destruction of graphene chemical constitution；Simultaneously as introduce pyrene functional group in initiator, reduce graphene subtract it is viscous
Attached power, moreover it is possible to introduce more functional groups using polymer chain to realize the non-covalent modification of graphene surface with it is multi-functional
Change.
The second aspect of the invention provides a kind of method preparing above-mentioned initiator, with pyrene butanol and 5- norborneols
Alkene -2- carboxylic acids are raw material, using dicyclohexylcarbodiimide and 4-dimethylaminopyridine as catalyst system and catalyzing, are after carrying out esterification
It can get the ring-opening metathesis polymerization initiator containing pyrene functional group.
The third aspect of the invention provides a kind of preparation method of graphene/poly ion liquid composite material, will be upper
The graphene that initiator is modified, the stone modified with initiator are obtained after stating initiator and graphene dispersion in a solvent a period of time
It is poly- that poly ion liquid monomer progress ring-opening metathesis is added as catalyst as initiator, Grubbs second generations catalyst in black alkene
Conjunction can be obtained graphene/poly ion liquid composite material.
It is compound to provide a kind of graphene/poly ion liquid that above-mentioned preparation method obtains for the fourth aspect of the invention
Material.
The fifth aspect of the invention provides a kind of above-mentioned graphene/poly ion liquid composite material in capacitor, light
Application in electrical part, energy-storage battery, electrochemical sensor, antibacterial.
Beneficial effects of the present invention are：
1. non-covalent π-π of the present invention by the pyrene functional group in initiator and between graphene is acted on polymer chain
One end is fixed on graphene, so as to avoid the destruction to graphene chemical constitution.
2. non-covalent π-π of the present invention by the pyrene functional group in initiator and between graphene is acted on polymer chain
One end is fixed on graphene, and contains more functional groups using polymer chain, can not only more effectively reduce graphene
Between adhesion strength, and can be made according to the difference of introduced functional group graphene surface have different functionality, realize stone
The non-covalent modification on black alkene surface and multifunction, the advantage with bigger.
Description of the drawings
The accompanying drawings which form a part of this application are used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation do not constitute the improper restriction to the application for explaining the application.
Fig. 1 is the infrared spectrogram of graphene and graphene/poly ion liquid composite material in the present invention；
Fig. 2 is the x-ray photoelectron spectroscopy of graphene/poly ion liquid composite material in the present invention.
Specific implementation mode
It is noted that described further below be all exemplary, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific implementation mode, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or combination thereof.
As background technology is introduced, covalence graft method, which exists in the prior art, can destroy the original chemistry knot of graphene
Structure, the deficiency of mechanical performance, electrical property to influence graphene etc., in order to solve technical problem as above, the application is a kind of
Graphene/poly ion liquid composite material and preparation method and application.
A kind of exemplary embodiment of the application provides a kind of ring-opening metathesis polymerization (ROMP) containing pyrene functional group and draws
Agent is sent out, structural formula is：
Initiator Zhong Bi functional groups can be acted on by non-covalent π-π and polymer one end is fixed on graphene, from
And avoid the destruction of graphene chemical constitution；Simultaneously as introduce pyrene functional group in initiator, reduce graphene subtract it is viscous
Attached power, moreover it is possible to introduce more functional groups using polymer chain to realize the non-covalent modification of graphene surface with it is multi-functional
Change.
Another embodiment of the invention provides a kind of method preparing above-mentioned initiator, is dropped with pyrene butanol and 5-
Bornylene -2- carboxylic acids are raw material, using dicyclohexylcarbodiimide and 4-dimethylaminopyridine as catalyst system and catalyzing, carry out esterification
It can be obtained the ring-opening metathesis polymerization initiator containing pyrene functional group afterwards.
Preferably, step is：Dicyclohexylcarbodiimide is added to containing by pyrene butanol, 4-dimethylaminopyridine and 5-
In the dichloromethane solution of norbornene -2- carboxylic acids, in anhydrous condition, at room temperature stir a period of time after can be obtained initiation
Agent.The room temperature refers to that temperature is 15~30 DEG C.It is further preferred that the mixing time is 24~36h.
It is further preferred that dicyclohexylcarbodiimide, pyrene butanol, 4-dimethylaminopyridine and 5- norbornene -2- carboxylics
The molar ratio of acid is 1.0~1.2:0.9~1.1:0.04~0.06:1.
In order to improve the purity for obtaining initiator, it is further preferred that the purification process after stirring is：It evaporates under vacuum
Afterwards, crude reaction product is passed through into post separation, the anhydrous MgSO of extraction organic phase4It is dry, vacuum distillation.
The third of the application embodiment there is provided a kind of preparation method of graphene/poly ion liquid composite material,
The graphene of initiator modification will be obtained after above-mentioned initiator and graphene dispersion in a solvent a period of time, modified with initiator
Graphene as initiator, Grubbs second generations catalyst is as catalyst, and poly ion liquid monomer is added, and to carry out open loop easy
Position polymerization can be obtained graphene/poly ion liquid composite material.
The existing product of Grubbs second generation catalyst described herein, No. CAS is：246047-72-3.
Preferably, the mass ratio of initiator and graphene is 1.5~2.5:1.
Preferably, the step of ring-opening metathesis polymerization is：The graphene of initiator modification and the Grubbs second generations are urged
Agent is added in solvent, is reacted under atmosphere of inert gases, and excessive catalyst is removed, and obtains the centre containing Ru functional groups
Intermediate containing Ru functional groups is added in the solution of poly ion liquid monomer by body, after being reacted under atmosphere of inert gases
It can be obtained graphene/poly ion liquid composite material.
The inert gas is the gas, such as argon gas, nitrogen etc. for referring to prevent raw material from carrying out oxidation reaction.
It is further preferred that the graphene and 10mg Grubbs second generation catalyst of initiator modification are added to 5mL dichloros
It in dichloromethane, is reacted under Ar after twenty minutes, removes excessive catalyst with dichloromethane, obtain containing Ru functional groups
0.25M poly ion liquid monomers are dissolved in 5mL dichloromethane solutions, add the intermediate containing Ru functional groups by intermediate,
Polymerisation carries out at room temperature under Ar protections, and centrifuge washing drying obtains graphene/poly ion liquid composite material.
The thickness of poly ion liquid brush can be controlled in polymerisation by changing polymerization time.
The poly ion liquid monomer is 1- norborny methylene -3- methyl imidazolium bromides (NM-MIm-Br), 1-
Norborny methylene -3- methylimidazole hexafluorophosphates (NM-MIm-PF6), 1- norborny methylene -3- methylimidazoles
Tetrafluoroborate (NM-MIm-BF4), these poly ion liquid monomers can according to document (J.Mater.Chem., 2012,
22,13123) it is synthesized into.
Embodiment there is provided a kind of graphene/poly ion liquids that above-mentioned preparation method obtains by the 4th of the application
Composite material.
Embodiment there is provided a kind of above-mentioned graphene/poly ion liquid composite materials in capacitance by the 5th of the application
Application in device, photoelectric device, energy-storage battery, electrochemical sensor, antibacterial.
In order to enable those skilled in the art can clearly understand the technical solution of the application, below with reference to tool
The technical solution of the application is described in detail with comparative example for the embodiment of body.
Embodiment 1：
(1) preparation of ring-opening metathesis polymerization (ROMP) initiator containing pyrene functional group, the specific steps are：By dicyclohexyl
Carbodiimide (DCC) (2.27g, 11mmol) is added to containing by pyrene butanol (1.89g, 10mmol), 4-dimethylaminopyridine
(DMAP) in the dichloromethane solution of (61mg, 0.5mmol) and 5- norbornene -2- carboxylic acids (1.38g, 10mmol).It will reaction
Mixture is stirred at room temperature for 24 hours in anhydrous conditions.After evaporating under vacuum, crude reaction product is passed through into post separation, extraction
The anhydrous MgSO of organic phase4Dry, vacuum distillation obtains Off-white solid.
(2) initiator non-covalent modification graphene, the specific steps are：The dichloromethane of the above-mentioned prepared initiators of 2mg/mL
50mg graphenes are added in solution (50mL), are stirred at room temperature for 24 hours, centrifuge washing drying.
(3) ring-opening metathesis polymerization (SI-ROMP) is caused on surface, the specific steps are：By initiator modification graphene and
10mg Grubbs second generation catalyst is added in 5mL dichloromethane solutions, is reacted under Ar after twenty minutes, is carefully used dichloro
Methane is rinsed to remove excessive catalyst, obtains [Ru] functionalized sample.By 0.25M 1- norborny methylene -3- first
Base limidazolium hexafluorophosphate (NM-MIm-PF6) be dissolved in 5mL dichloromethane solutions, [Ru] functionalized sample is added, is gathered
It closes reaction and carries out 15min at room temperature under Ar protections, centrifuge washing drying obtains graphene/poly ion liquid composite material.Its
Shown in infrared spectrogram such as Fig. 1 (b), compared with the infrared spectrum (Fig. 1 (a)) of graphene, the curve of Fig. 1 is visible in 3200-
3090cm-1And 3000-2850cm-1Place is poly- (1- norborny methylene -3- methylimidazoles hexafluorophosphate) (PNM-
MIm-PF6) absorption band, this is attributable to the C-H stretching vibration absworption peaks of imidazole ring；In 1575,1460 and 1170cm-1Place is
The eigen vibration band of alkyl chain corresponds to imidazole ring cation；In 841cm-1The strong absworption peak at place is attributed to PF6 ﹣In P-F
Stretching vibration absworption peak shows that graphene surface has succeeded grafted polymer.The x-ray photoelectron spectroscopy of the composite material is such as
Shown in Fig. 2, after being grafted poly ion liquid, there is the peaks N, the peaks F and the peaks P of feature in ionic liquid.From the above two width figure
As can be seen that the method for the present invention can successfully obtain graphene/poly ion liquid composite material.
Embodiment 2：
(1) preparation of ring-opening metathesis polymerization (ROMP) initiator containing pyrene functional group, the specific steps are：By dicyclohexyl
Carbodiimide (DCC) (2.27g, 11mmol) is added to containing by pyrene butanol (1.89g, 10mmol), 4-dimethylaminopyridine
(DMAP) in the dichloromethane solution of (61mg, 0.5mmol) and 5- norbornene -2- carboxylic acids (1.38g, 10mmol).It will reaction
Mixture is stirred at room temperature for 24 hours in anhydrous conditions.After evaporating under vacuum, crude reaction product is passed through into post separation, extraction
The anhydrous MgSO of organic phase4Dry, vacuum distillation obtains Off-white solid.
(2) initiator non-covalent modification graphene, the specific steps are：The dichloromethane of the above-mentioned prepared initiators of 2mg/mL
50mg graphenes are added in solution (50mL), are stirred at room temperature for 24 hours, centrifuge washing drying.
(3) ring-opening metathesis polymerization (SI-ROMP) is caused on surface, the specific steps are：By initiator modification graphene and
10mg Grubbs second generation catalyst is added in 5mL dichloromethane solutions, is reacted under Ar after twenty minutes, is carefully used dichloro
Methane is rinsed to remove excessive catalyst, obtains [Ru] functionalized sample.By 0.25M 1- norborny methylene -3- first
Base limidazolium hexafluorophosphate (NM-MIm-PF6) be dissolved in 5mL dichloromethane solutions, [Ru] functionalized sample is added, is gathered
It closes reaction and carries out 2h at room temperature under Ar protections, centrifuge washing drying obtains graphene/poly ion liquid composite material.
Embodiment 3：
(1) preparation of ring-opening metathesis polymerization (ROMP) initiator containing pyrene functional group, the specific steps are：By dicyclohexyl
Carbodiimide (DCC) (2.27g, 11mmol) is added to containing by pyrene butanol (1.89g, 10mmol), 4-dimethylaminopyridine
(DMAP) in the dichloromethane solution of (61mg, 0.5mmol) and 5- norbornene -2- carboxylic acids (1.38g, 10mmol).It will reaction
Mixture is stirred at room temperature for 24 hours in anhydrous conditions.After evaporating under vacuum, crude reaction product is passed through into post separation, extraction
The anhydrous MgSO of organic phase4Dry, vacuum distillation obtains Off-white solid；
(2) initiator non-covalent modification graphene, the specific steps are：The dichloromethane of the above-mentioned prepared initiators of 2mg/mL
50mg graphenes are added in solution (50mL), are stirred at room temperature for 24 hours, centrifuge washing drying.
(3) ring-opening metathesis polymerization (SI-ROMP) is caused on surface, the specific steps are：By initiator modification graphene and
10mg Grubbs second generation catalyst is added in 5mL dichloromethane solutions, is reacted under Ar after twenty minutes, is carefully used dichloro
Methane is rinsed to remove excessive catalyst, obtains [Ru] functionalized sample.By 0.25M 1- norborny methylene -3- first
Base imidazolium bromide (NM-MIm-Br) is dissolved in 5mL dichloromethane solutions, adds [Ru] functionalized sample, and polymerization is anti-
It should carry out 15min at room temperature under Ar protections, centrifuge washing drying obtains graphene/poly ion liquid composite material.
Embodiment 4：
(1) preparation of ring-opening metathesis polymerization (ROMP) initiator containing pyrene functional group, the specific steps are：By dicyclohexyl
Carbodiimide (DCC) (2.27g, 11mmol) is added to containing by pyrene butanol (1.89g, 10mmol), 4-dimethylaminopyridine
(DMAP) in the dichloromethane solution of (61mg, 0.5mmol) and 5- norbornene -2- carboxylic acids (1.38g, 10mmol).It will reaction
Mixture is stirred at room temperature for 24 hours in anhydrous conditions.After evaporating under vacuum, crude reaction product is passed through into post separation, extraction
The anhydrous MgSO of organic phase4Dry, vacuum distillation obtains Off-white solid；
(2) initiator non-covalent modification graphene, the specific steps are：The dichloromethane of the above-mentioned prepared initiators of 2mg/mL
50mg graphenes are added in solution (50mL), are stirred at room temperature for 24 hours, centrifuge washing drying.
(3) ring-opening metathesis polymerization (SI-ROMP) is caused on surface, the specific steps are：By initiator modification graphene and
10mg Grubbs second generation catalyst is added in 5mL dichloromethane solutions, is reacted under Ar after twenty minutes, is carefully used dichloro
Methane is rinsed to remove excessive catalyst, obtains [Ru] functionalized sample.By 0.25M 1- norborny methylene -3- first
Base tetrafluoroborate (NM-MIm-BF4) be dissolved in 5mL dichloromethane solutions, [Ru] functionalized sample is added, is gathered
It closes reaction and carries out 15min at room temperature under Ar protections, centrifuge washing drying obtains graphene/poly ion liquid composite material.
The foregoing is merely the preferred embodiments of the application, are not intended to limit this application, for the skill of this field
For art personnel, the application can have various modifications and variations.Within the spirit and principles of this application, any made by repair
Change, equivalent replacement, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of ring-opening metathesis polymerization initiator containing pyrene functional group, characterized in that structural formula is：
2. a kind of method preparing initiator described in claim 1, characterized in that with pyrene butanol and 5- norbornene -2- carboxylics
Acid is raw material, using dicyclohexylcarbodiimide and 4-dimethylaminopyridine as catalyst system and catalyzing, be can be obtained after carrying out esterification
Ring-opening metathesis polymerization initiator containing pyrene functional group.
3. method as claimed in claim 2, characterized in that step is：Dicyclohexylcarbodiimide is added to containing by pyrene
In the dichloromethane solution of butanol, 4-dimethylaminopyridine and 5- norbornene -2- carboxylic acids, in anhydrous condition, at room temperature stir
It can be obtained initiator after a period of time.
4. method as claimed in claim 3, characterized in that dicyclohexylcarbodiimide, pyrene butanol, 4-dimethylaminopyridine and
The molar ratio of 5- norbornene -2- carboxylic acids is 1.0~1.2:0.9~1.1:0.04~0.06:1.
5. a kind of preparation method of graphene/poly ion liquid composite material, characterized in that by initiation described in claim 1
The graphene that initiator modification is obtained after agent and graphene dispersion in a solvent a period of time, is made with the graphene of initiator modification
For initiator, Grubbs second generations catalyst is added poly ion liquid monomer and carries out ring-opening metathesis polymerization as catalyst
Obtain graphene/poly ion liquid composite material.
6. preparation method as claimed in claim 5, characterized in that the mass ratio of initiator and graphene is 1.5~2.5:1.
7. preparation method as claimed in claim 5, characterized in that the step of ring-opening metathesis polymerization is：Initiator is repaiied
The graphene and Grubbs second generation catalyst of decorations are added in solvent, are reacted under atmosphere of inert gases, are removed excessive catalysis
Agent obtains the intermediate containing Ru functional groups, and the intermediate containing Ru functional groups is added to the solution of poly ion liquid monomer
In, it can be obtained graphene/poly ion liquid composite material after being reacted under atmosphere of inert gases.
8. preparation method as claimed in claim 7, characterized in that the graphene and 10mg Grubbs second of initiator modification
It is added in 5mL dichloromethane solutions, is reacted under Ar after twenty minutes for catalyst, excessive catalysis is removed with dichloromethane
Agent obtains the intermediate containing Ru functional groups, and 0.25M poly ion liquid monomers are dissolved in 5mL dichloromethane solutions, are added
Intermediate containing Ru functional groups, polymerisation carry out at room temperature under Ar protections, centrifuge washing drying, obtain graphene/poly-
Ionic liquid composite material.
9. graphene/poly ion liquid composite material that a kind of any preparation method of claim 5~8 obtains.
10. graphene/poly ion liquid composite material described in a kind of claim 9 is in capacitor, photoelectric device, energy storage electricity
Application in pond, electrochemical sensor, antibacterial.
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| WO2024031541A1 (en) * | 2022-08-11 | 2024-02-15 | 江苏卫星新材料股份有限公司 | Method for preparing multifunctional graphene oxide and method for preparing pvcpvdf composite film |
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| WO2024031541A1 (en) * | 2022-08-11 | 2024-02-15 | 江苏卫星新材料股份有限公司 | Method for preparing multifunctional graphene oxide and method for preparing pvcpvdf composite film |
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